Trimethylsilyl cyanide promoted cyanation of tertiary alkyl chlorides and other SN1 active compounds

Farewell to the HSAB Treatment of Ambident Reactivity

“…[30] The formation of 1-isocyanoadamantane from 1-chloroadamantane and trimethylsilyl cyanide in the presence of TiCl 4 (Scheme 7) demonstrates that blocking of the carbon atom of cyanide is not restricted to Ag + . [32] Exclusive formation of nitriles, which is well known for reactions of primary alkyl bromides and alkyl iodides with NaCN and KCN, has also been observed for the methylation of [Bu 4 …”

Lewis Acid Catalyzed Synthesis of Cyanidophosphates

“…for the analogous Me 3 Si‐NC‐B(CN) 3 species . Interestingly, the formation of Ph 3 CCN was reported before in the reaction of [Ph 3 C][BF 4 ] with Me 3 SiCN, which yields intermediate nitrilium ions of the type [Ph 3 C‐NC‐SiMe 3 ] + or [Ph 3 C‐NC‐CPh 3 ] + (see below) . Since in the tritylium reaction only “Me 3 Si + ” remained as formal cation for the [PF 2 (CN) 4 ] − ion, we stopped this reaction by quenching with one equivalent of [ n Bu 4 N]Cl (Scheme ), which gave after workup [ n Bu 4 N][PF 2 (CN) 4 ] at ambient temperature (besides Me 3 SiCl).…”

“…[17] Interestingly,t he formationo f Ph 3 CCN was reportedb efore in the reaction of [Ph 3 C][BF 4 ]w ith Me 3 SiCN, which yields intermediate nitrilium ions [18] of the type [Ph 3 C-NC-SiMe 3 ] + or [Ph 3 C-NC-CPh 3 ] + (see below). [19,20] Since in the tritylium reactiono nly "Me 3 Si + "r emained as formal cation for the [PF 2 (CN) 4 ] À ion, we stopped this reactionb yq uenching with one equivalent of [nBu 4 N]Cl (Scheme3), which gave after workup[ nBu 4 N][PF 2 (CN) 4 ]a ta mbient temperature (besides Me 3 SiCl). Since this reaction is rather violent at 25 8C, we studied the influence of the temperature on the product distribution in detail (Table 1).…”

Deuterium Quantification through Deuterium‐Induced Remote1H and13C NMR Shifts

“…Scheme displays the formulae of the investigated compounds 1 – 6 with their deuterium‐induced 1 H and 13 C NMR isotope shifts Δ in units of ppb (=10 −3 ppm). We prepared perdeuteriopivalonitrile ( 1 ) from commercial (D 3 C) 3 CCl by the one‐step method4 (yield 22 %),5 and converted it into tert ‐butyl [D 9 ] tert ‐butyl ketone ( 2 ) using a Barbier‐type procedure 6. Compounds 3 – 6 were studied as mixtures7 of these isotopomers ( 3 / 4 and 5 / 6 ) and isotopologues ( 3 being the main component) with the parent unlabeled acyloin (H 3 C) 3 CC(O)C(OH)[C(CH 3 ) 3 ] 2 , namely, 4‐ tert ‐butyl‐4‐hydroxy‐2,2,5,5‐tetramethylhexan‐3‐one.…”